JPH0288789A - Bismuth-tin alloy electroplating bath and plating method - Google Patents
Bismuth-tin alloy electroplating bath and plating methodInfo
- Publication number
- JPH0288789A JPH0288789A JP23830488A JP23830488A JPH0288789A JP H0288789 A JPH0288789 A JP H0288789A JP 23830488 A JP23830488 A JP 23830488A JP 23830488 A JP23830488 A JP 23830488A JP H0288789 A JPH0288789 A JP H0288789A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- bismuth
- salt
- bath
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 45
- 238000009713 electroplating Methods 0.000 title claims abstract description 11
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 26
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 150000001621 bismuth Chemical class 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 abstract description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000174 gluconic acid Substances 0.000 abstract description 4
- 235000012208 gluconic acid Nutrition 0.000 abstract description 4
- -1 Bi2(SO4)3 Chemical class 0.000 abstract description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 abstract description 2
- 229910016338 Bi—Sn Inorganic materials 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- YCELPWGPXSJYMB-OWOJBTEDSA-N (e)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(/C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-OWOJBTEDSA-N 0.000 description 1
- YCELPWGPXSJYMB-UPHRSURJSA-N (z)-2-sulfobut-2-enedioic acid Chemical compound OC(=O)\C=C(\C(O)=O)S(O)(=O)=O YCELPWGPXSJYMB-UPHRSURJSA-N 0.000 description 1
- MCXZBEZHTYZNRE-UHFFFAOYSA-N 1-chloropropane-1-sulfonic acid Chemical compound CCC(Cl)S(O)(=O)=O MCXZBEZHTYZNRE-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 1
- OURSFPZPOXNNKX-UHFFFAOYSA-N 3-sulfopropanoic acid Chemical compound OC(=O)CCS(O)(=O)=O OURSFPZPOXNNKX-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- RMPWRUZQAKINCP-OPDGVEILSA-K bismuth;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Bi+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RMPWRUZQAKINCP-OPDGVEILSA-K 0.000 description 1
- MNMKEULGSNUTIA-UHFFFAOYSA-K bismuth;methanesulfonate Chemical compound [Bi+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MNMKEULGSNUTIA-UHFFFAOYSA-K 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 239000000182 glucono-delta-lactone Substances 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- PQGFRBOHUKOXQZ-FSCNPAMSSA-J tris[[(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanoyl]oxy]stannyl (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Sn+4].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O PQGFRBOHUKOXQZ-FSCNPAMSSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ビスマス量が３０〜５５％（重量％、以下同
じ）の低融点ビスマス−錫合金電気めっき皮膜を形成す
ることができるビスマス−錫合金電気めっき浴及びめっ
き方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a bismuth-tin alloy that can form a low melting point bismuth-tin alloy electroplated film containing 30 to 55% (by weight, the same shall apply hereinafter) of bismuth. This invention relates to a tin alloy electroplating bath and a plating method.
従来、電子部品に半田付けを行なうような場合。 Traditionally, when soldering electronic components.
錫めっきや錫−鉛合金めっきを施すことが行なわれてい
るが、最近半田付けのためにビスマス−錫（Ｂｉ−８ｎ
）合金めっきが要望されている。Tin plating and tin-lead alloy plating are used, but recently bismuth-tin (Bi-8n) is used for soldering.
) Alloy plating is required.
このＢ１−８ｎ合金めっき法としては、従来、硫酸浴、
有機スルホン酸浴などが知られている（特開昭６３−１
４８８７号公報）。Conventionally, this B1-8n alloy plating method uses a sulfuric acid bath,
Organic sulfonic acid baths are known (Japanese Unexamined Patent Publication No. 1986-1
Publication No. 4887).
しかし、これらの硫酸浴及び有機スルホン酸浴は、いず
れもビスマスが貴の金属であるため、浴中のビスマスイ
オンが置換反応を起こし易く、被めっき物を浴中に浸漬
するとき或いはＢ１−８ｎ合金めっきが施された被めっ
き物を浴から引き上げるとき、被めっき物が通電されて
いないと被めっき物やその表面に電気めっきされたＢ１
−５ｎ皮膜上にＢｉが置換析出する。また、Ｂ１−８ｎ
合金陽極上にも非通電時にＢｉが置換析出する。However, in both of these sulfuric acid baths and organic sulfonic acid baths, since bismuth is a noble metal, the bismuth ions in the baths tend to undergo a substitution reaction, and when the object to be plated is immersed in the baths, B1-8n When removing an alloy-plated object from the bath, if the object is not energized, electroplated B1 will be removed from the object or its surface.
- Bi is substituted and precipitated on the 5n film. Also, B1-8n
Bi is also substituted and precipitated on the alloy anode when no current is applied.
このように、被めっき物にめっき前にＢｉが置換析出す
ることは、その上にＢ１−Ｓｎ合金めっき皮膜が形成さ
れた場合、その密着を損ない、また得られたＢ ｉ −
Ｓ ｎ合金めっき皮膜上にＢｉが置換析出することは、
Ｂ１−Ｓｎ合金めっき皮膜の特性を損なう。更に、Ｂ１
−Ｓｎ合金陽極にＢｉが置換析出することは、めっき作
業を困難にする。しかも、Ｂｉが置換析出した場合、こ
れによって消費したＢｉを補給しなければならない。As described above, the substitutional precipitation of Bi before plating on the object to be plated impairs its adhesion when a B1-Sn alloy plating film is formed thereon, and the resulting Bi -
The substitutional precipitation of Bi on the Sn alloy plating film is due to the following:
The characteristics of the B1-Sn alloy plating film are impaired. Furthermore, B1
The substitutional precipitation of Bi on the -Sn alloy anode makes plating work difficult. Furthermore, when Bi is substituted and precipitated, the consumed Bi must be replenished.
このため、被めっき物或いはその上に形成されたＢ１−
Ｓｎ合金めっき皮膜へのＢｉの置換を防止する対策とし
て、被めっき物を浴中に浸漬するとき及び浴中から引き
上げるときに被めっき物を通電することが必要となる。Therefore, the B1-
As a measure to prevent substitution of Bi into the Sn alloy plating film, it is necessary to energize the object to be plated when it is immersed in the bath and when it is lifted out of the bath.
また、Ｂ ｉ −Ｓ ｎ合金陽極はめっき作業の終了と
同時に浴から引き上げ、めっき作業の開始時に再び浴中
に吊り下げるという作業が必要となり、かなりの手間を
要する。Furthermore, it is necessary to take the B i -S n alloy anode out of the bath at the same time as the plating operation ends, and suspend it again in the bath at the start of the plating operation, which requires considerable effort.
また、従来の硫酸浴は浴の安定性が悪く、しかもビスマ
ス塩の溶解度が低いので、Ｂｉ量の低いＢ１−Ｓｎ合金
めっき皮膜しか得られず、低融点とならないという問題
がある。Furthermore, conventional sulfuric acid baths have poor bath stability and low solubility of bismuth salts, resulting in the problem that only B1-Sn alloy plating films with a low amount of Bi can be obtained and do not have a low melting point.
一方、有機スルホン酸浴として、上述したように特開昭
６３−１４８８７号公報に記載のものが知られているが
、これに開示されたＢ１−Ｓｎ合金めっき浴からは電流
密度が０ 、３ Ａ ／ｄｍ”以下でＢｉ量が３０％以
上のＢ１−Ｓｎ合金めっき皮膜は得られていない。On the other hand, as mentioned above, the organic sulfonic acid bath described in JP-A-63-14887 is known, but the B1-Sn alloy plating bath disclosed therein has a current density of 0, 3. A B1-Sn alloy plating film with a Bi content of 30% or more at A/dm" or less has not been obtained.
本発明は、上記事情に鑑みなされたもので、Ｂｉ量が多
く、低融点のＢ１−Ｓｎ合金めっき皮膜を低電流密度か
ら高電流密度の広い範囲に亘って確実に得ることができ
、また、非通電時において被めっき物やＢ ｉ −Ｓ
ｎ合金陽極にＢｉの置換析出のないＢ１−Ｓｎ合金電気
めっき浴及びめっき方法を提供することを目的とする。The present invention was made in view of the above circumstances, and it is possible to reliably obtain a B1-Sn alloy plating film with a large amount of Bi and a low melting point over a wide range of current densities from low current densities to high current densities, and, When the current is not applied, the plated object and Bi-S
It is an object of the present invention to provide a B1-Sn alloy electroplating bath and a plating method that do not cause substitutional precipitation of Bi on an n-alloy anode.
〔課題を解決するための手段及び作用〕本発明者は、上
記目的を達成するため鋭意検討を行なった結果、ビスマ
ス塩と、２価の錫塩と、該錫塩を溶解する酸、例えば硫
酸、有機スルホン酸等とを含有するめっき浴に対し、更
にグルコン酸等のオキシカルボン酸を添加すること、ま
たこのようなオキシカルボン酸添加浴中のビスマスと２
価の錫との含有割合を１：１〜１０：１とすることによ
り、Ｂｉ量が３０〜５５％の高Ｂｉ量のＢ１−Ｓｎ合金
電気めっき皮膜を形成することが可能になり、しかもこ
の浴は低電流密度でもめっき皮膜中にＢｉが入り易く、
バレルめっきにおいても高Ｂｉ量で低融点のＢ１−Ｓｎ
合金めっき皮膜が得られることを知見した。更に、この
浴はＢｉの置換析出が生じ難く、被めっき物を通電しな
がら浴中に浸漬したり浴中から引き上げたりしなくとも
被めっき物或いはＢ１−Ｓｎ合金めっき皮膜上にＢｉが
置換析出せず、またＢ１−Ｓｎ合金陽極やＳｎ陽極にも
非通電時にＢｉの置換析出がなく、このため作業終了時
に陽極を浴から引き上げるような必要がなく、従って作
業性が良好であることを見い出し、本発明をなすに至っ
た。[Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the inventors of the present invention have discovered that a bismuth salt, a divalent tin salt, and an acid that dissolves the tin salt, such as sulfuric acid. , an organic sulfonic acid, etc., to a plating bath containing oxycarboxylic acid such as gluconic acid, and bismuth and 2.
By setting the content ratio of valent tin to 1:1 to 10:1, it is possible to form a B1-Sn alloy electroplated film with a high Bi content of 30 to 55%. Bi easily enters the plating film even at low current density in the bath.
B1-Sn with high Bi content and low melting point even in barrel plating
It was discovered that an alloy plating film could be obtained. Furthermore, this bath is difficult to cause substitutional precipitation of Bi, and Bi can be substituted and precipitated on the plated object or the B1-Sn alloy plating film without immersing the plated object in the bath while applying electricity or removing it from the bath. Furthermore, it was discovered that there was no substitutional precipitation of Bi on the B1-Sn alloy anode or the Sn anode when the current was not applied, and therefore there was no need to remove the anode from the bath at the end of the work, and the workability was therefore good. , the present invention was accomplished.
従って、本発明は、ビスマス塩と、２価の錫塩と、該錫
塩を溶解する酸と、オキシカルボン酸とを含有し、かつ
ビスマスと２価の錫との含有割合が重量比として１：１
〜１０：１であることを特＝４−
徴とするビスマス−錫合金電気めっき浴及び該めっき浴
を用いて被処理物に電気めっきを施し、該被処理物にビ
スマス量が３０〜５５重量％のビスマス−錫合金めっき
皮膜を形成することを特徴とするビスマス−錫合金電気
めっき方法を提供する。Therefore, the present invention contains a bismuth salt, a divalent tin salt, an acid that dissolves the tin salt, and an oxycarboxylic acid, and the content ratio of bismuth and divalent tin is 1 by weight. :1
A bismuth-tin alloy electroplating bath having a characteristic of ~10:1 and electroplating a workpiece using the plating bath, and a bismuth amount of 30 to 55% by weight on the workpiece. % bismuth-tin alloy electroplating method is provided.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明浴において使用されるビスマス塩としては、硫酸
ビスマス、メタンスルホン酸ビスマス。Bismuth salts used in the bath of the present invention include bismuth sulfate and bismuth methanesulfonate.
フェノールスルホン酸ビスマス等の有機スルホン酸ビス
マス、グルコン酸ビスマスなどが挙げられる。また、第
１細塩としては、硫酸錫、塩化錫。Examples include bismuth organic sulfonates such as bismuth phenolsulfonate, bismuth gluconate, and the like. Further, as the first fine salt, tin sulfate and tin chloride are used.
有機スルホン酸錫、グルコン酸錫などが挙げられる。Examples include tin organic sulfonate and tin gluconate.
これらビスマス塩、第１Ｍ塩の浴中の含有量は種々選定
されるが、ビスマス塩はビスマスとして５〜３０ ｇ
／ Ｑ、特ニ８〜２０ ｇ ／ ａとすることが好まし
く、第１錫塩は錫として１〜６ ｇ ／ Ｑ、特に２〜
５ｇ／Ｑとすることが好ましい。この場合、ビスマスと
２価の錫との含有割合は、重量比として１：１〜１０：
１、特に２：１〜６：１とするもので、これにより高Ｂ
ｉ量で低融点のＢ１−８ｎ合金めっき皮膜を得ることが
できる。これに対し、ビスマス量が上記範囲より少ない
場合は、ビスマスの析出量が少なくなって低融点のＢ１
−８ｎ合金めっき皮膜が得難くなり、またビスマス量が
多くなり過ぎると、ビスマスの共析量が共晶点よりも多
くなり過ぎて、かえって低融点皮膜が得られない場合が
生じる。また、金属（ビスマスと２価の錫）の総合有量
は６〜３６ｇ７ｍ、特に１０〜２５ｇ／Ｑとすることが
好ましく、金属総量をかかる範囲とすることにより、低
電流密度部でも高Ｂｉ量のＢ１−８ｎ合金めっき皮膜が
より確実に形成し得る。The content of these bismuth salts and 1M salts in the bath is variously selected, but the content of bismuth salts is 5 to 30 g as bismuth.
/Q, preferably 8 to 20 g/a, and the stannous salt has a tin content of 1 to 6 g/Q, especially 2 to 20 g/a.
It is preferable to set it as 5g/Q. In this case, the content ratio of bismuth and divalent tin is 1:1 to 10:
1, especially 2:1 to 6:1, which results in high B
A B1-8n alloy plating film with a low melting point can be obtained with an amount of i. On the other hand, if the amount of bismuth is less than the above range, the amount of bismuth precipitated will be small, resulting in a low melting point of B1.
It becomes difficult to obtain a -8n alloy plating film, and if the amount of bismuth is too large, the amount of bismuth eutectoid becomes too large than the eutectic point, and a low melting point film may not be obtained. In addition, the total amount of metals (bismuth and divalent tin) is preferably 6 to 36 g/Q, particularly 10 to 25 g/Q. By setting the total amount of metals within this range, even in low current density areas, the amount of Bi is high. A B1-8n alloy plating film can be formed more reliably.
また、第１錫塩を溶解する酸としては、硫酸、塩酸、硝
酸等の無機酸、それに有機スルホン酸などが挙げられる
。この場合、有機スルホン酸としては、置換又は未置換
のアルカンスルホン酸、ヒドロキシアルカンスルホン酸
、ベンゼンスルホン酸、ナフタレンスルホン酸などを挙
げることができる。Further, examples of acids that dissolve stannous salts include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic sulfonic acids. In this case, examples of the organic sulfonic acid include substituted or unsubstituted alkanesulfonic acids, hydroxyalkanesulfonic acids, benzenesulfonic acids, naphthalenesulfonic acids, and the like.
ここで、未置換のアルカンスルホン酸としてはＣｎＨ２
ｎ＋１ＳＯ３Ｈ
（但し、ｎは１〜５、好ましくは１又は２である）で示
されるものが使用でき、未置換のヒドロキシアルカンス
ルホン酸としては
Ｈ
Ｃ，Ｈ，、＋、−ＣＨ−ＣｊＨ，，＋１−８ｏ３Ｈ（但
し、ｍは０〜２、Ｑは１〜３である）で示されるものが
使用できる。また、置換アルカンスルホン酸、ヒドロキ
シアルカンスルホン酸としてはそのアルキル基の水素原
子の一部がハロゲン原子、アリール基、アルキルアリー
ル基、カルボキシル基、スルホン酸基などで置換された
ものが使用できる。一方、ベンゼンスルホン酸、ナフタ
レンスルホン酸は、下記式
で示されるものであるが、置換ベンゼンスルホン酸、ナ
フタレンスルホン酸としては、ベンゼン環、ナフタレン
環の水素原子の一部が水酸基、ハロゲン原子、アルキル
基、カルボキシル基、ニトロ基、メルカプト基、アミノ
基、スルホン酸基などで置換されたものが使用できる。Here, as the unsubstituted alkanesulfonic acid, CnH2
Those represented by n+1SO3H (where n is 1 to 5, preferably 1 or 2) can be used, and unsubstituted hydroxyalkanesulfonic acids include H C, H,, +, -CH-CjH,, +1 -8o3H (where m is 0 to 2 and Q is 1 to 3) can be used. Further, as substituted alkanesulfonic acids and hydroxyalkanesulfonic acids, those in which a portion of the hydrogen atoms of the alkyl groups are substituted with halogen atoms, aryl groups, alkylaryl groups, carboxyl groups, sulfonic acid groups, etc. can be used. On the other hand, benzenesulfonic acid and naphthalenesulfonic acid are represented by the following formula, but in substituted benzenesulfonic acid and naphthalenesulfonic acid, some of the hydrogen atoms in the benzene ring and naphthalene ring are hydroxyl groups, halogen atoms, alkyl Those substituted with a group, a carboxyl group, a nitro group, a mercapto group, an amino group, a sulfonic acid group, etc. can be used.
具体的には、有機カルボン酸として、メタンスルホン酸
、エタンスルホン酸、プロパンスルホン酸、２−プロパ
ンスルホン酸、ブタンスルホン酸、２−ブタンスルホン
酸、ペンタンスルホン酸、クロルプロパンスルホン酸、
２−ヒドロキシエタン−１−スルホン酸、２−ヒドロキ
シプロパン−１−スルホン酸、２−ヒドロキシブタン−
１−スルホン酸、２−ヒドロキシペンタンスルホン酸、
アリルスルホン酸、２スルホ酢酸、２−又は３−スルホ
プロピオン酸。Specifically, the organic carboxylic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, chloropropanesulfonic acid,
2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-
1-sulfonic acid, 2-hydroxypentanesulfonic acid,
Allylsulfonic acid, 2-sulfoacetic acid, 2- or 3-sulfopropionic acid.
スルホこはく酸、スルホマレイン酸、スルホフマル酸、
ベンゼンスルホン酸、トルエンスルホン酸、キシレンス
ルホン酸、ニトロベンゼンスルホン酸、スルホ安息香酸
、スルホサルチル酸、ベンズアルデヒドスルホン酸、ｐ
−フェノールスルホン酸などが例示され、これらの１種
又は２種以上を組み合せて用いることができる。Sulfosuccinic acid, sulfomaleic acid, sulfofumaric acid,
Benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, nitrobenzene sulfonic acid, sulfobenzoic acid, sulfosalcylic acid, benzaldehyde sulfonic acid, p
-phenolsulfonic acid is exemplified, and one or more of these can be used in combination.
上記酸の含有量も適宜選定されるが、浴中５０〜４００
ｇ／Ｑ、特に１００〜２００ ｇ ／ Ｑとすることが
好ましい。The content of the above acid is also selected appropriately, but it is 50 to 400% in the bath.
g/Q, particularly preferably 100 to 200 g/Q.
本発明浴には、更にオキシカルボン酸が含有されるが、
これらはオキシカルボン酸塩として添加してもよい。こ
こで、オキシカルボン酸としては、グルコン酸、グルコ
ノデルタラクトン、酒石酸。The bath of the present invention further contains oxycarboxylic acid,
These may be added as oxycarboxylic acid salts. Here, examples of oxycarboxylic acids include gluconic acid, glucono delta lactone, and tartaric acid.
クエン酸、コハク酸、マレイン酸、マロン酸、フマル酸
等が挙げられ、これらの１種を単独で又は２種以上を組
合せて使用できるが、これらの中ではグルコン酸が好ま
しい。オキシカルボン酸の含有量は２０〜２００ｇ／Ｑ
、特に３０〜１００ｇ／Ｑとすることが好ましく、その
含有量が少な過ぎるとビスマスを十分錯化し得す、水酸
化ビスマスの沈殿を生じる場合がある。逆に多過ぎると
結晶の微細化を阻害する場合がある。Examples include citric acid, succinic acid, maleic acid, malonic acid, fumaric acid, etc., and one type of these can be used alone or two or more types can be used in combination, but among these, gluconic acid is preferred. The content of oxycarboxylic acid is 20-200g/Q
In particular, it is preferably 30 to 100 g/Q; if the content is too low, bismuth may be sufficiently complexed and bismuth hydroxide may precipitate. On the other hand, if it is too large, crystal refinement may be inhibited.
本発明に係るめっき浴には、上記成分に加え、必要によ
りアルキルノニルフェニルエーテル等のノニオン界面活
性剤を添加することができ、かかる活性剤の添加により
均一かつ微細な結晶を得る一
ことができる。なお、上記活性剤の含有量は０．１〜２
０ ｇ ／ ｎ、特に４〜８ｇ／Ｑとすることが好適で
ある。更に、本発明浴にはゼラチン。In addition to the above components, a nonionic surfactant such as alkyl nonylphenyl ether can be added to the plating bath according to the present invention, if necessary, and uniform and fine crystals can be obtained by adding such an active agent. . In addition, the content of the above-mentioned activator is 0.1 to 2
It is suitable to set it as 0 g/n, especially 4-8 g/Q. Furthermore, the bath of the present invention contains gelatin.
ペプトン、その他の適宜な添加剤を添加することもでき
る。Peptone and other appropriate additives may also be added.
本発明のＢｊ−Ｓｎ合金電気めっき浴を用いてめっきを
行なう場合の条件としては、特に制限されるものではな
いが、陰極電流密度は０．１〜５Ａ ／ ｄｍ”とする
ことができ、めっき温度は１５〜３０℃を採用すること
ができる。また、撹拌は液流、カソードロッカー等の機
械的撹拌を採用し得る。陽極としては、Ｂ１−Ｓｎ合金
、Ｂｉ金金属Ｓｎ金属を用いることができ、場合によっ
ては白金付チタン板、カーボン等の不溶性陽極を用いる
ことができる。この場合、本発明浴はＢｉの置換析出が
生じ難いので、Ｂ１−Ｓｎ合金陽極、Ｓｎ陽極はめっき
作業終了後にそのまま浴中に放置しておくことができ、
放置したままでもこれら陽極表面にＢｉの置換膜は形成
されないものである。Conditions for plating using the Bj-Sn alloy electroplating bath of the present invention are not particularly limited, but the cathode current density can be 0.1 to 5 A/dm'', and the plating The temperature can be 15 to 30°C. Also, mechanical stirring such as liquid flow or cathode rocker can be used for stirring. B1-Sn alloy, Bi gold metal and Sn metal can be used as the anode. In some cases, an insoluble anode such as a platinized titanium plate or carbon may be used.In this case, since the bath of the present invention is unlikely to cause substitutional precipitation of Bi, the B1-Sn alloy anode or Sn anode may be used after the plating work is completed. You can leave it in the bath as it is,
Even if left as is, no Bi substitution film is formed on the surface of these anodes.
被めっき物は適宜選択されるが、本発明のめっき浴は上
述したようにＢｉの置換析出が生じ難いので、被めっき
物を浴中に浸漬する場合や浴中から引き上げる場合に非
通電状態で行なうことができる。The object to be plated is selected as appropriate, but since the plating bath of the present invention is unlikely to cause substitutional precipitation of Bi as described above, the object to be plated is not energized when immersed in the bath or removed from the bath. can be done.
なお、被めっき物はバレル法によりめっきすることもで
きる。Note that the object to be plated can also be plated by a barrel method.
本発明によれば、Ｂｉ量が３０〜５５％で、融点が１４
０〜１６０℃のＢ１−Ｓｎ合金めつき皮膜を広い電流密
度範囲に亘って形成することができ、またＢｉの置換析
出が防止されるので、作業が簡便化される。従って、本
発明は半田付を目的とした電子部品のめっき等に好適に
採用される。According to the present invention, the amount of Bi is 30 to 55% and the melting point is 14%.
A B1-Sn alloy plating film at 0 to 160° C. can be formed over a wide current density range, and substitutional precipitation of Bi is prevented, which simplifies the work. Therefore, the present invention is suitably employed in plating electronic components for the purpose of soldering.
以下、実施例を示し、本発明を具体的に説明するが、本
発明は下記の実施例に制限されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.
下記組成のめっき浴を調製し、下記条件でめっきを行な
った。得られためっき皮膜の外観及び皮膜中のＢｉ量を
下記に示す。A plating bath with the following composition was prepared, and plating was performed under the following conditions. The appearance of the obtained plating film and the amount of Bi in the film are shown below.
なお、比較例３，４の浴は被めっき物を浸漬するとＢｉ
の置換析出が生じたが、実施例の浴及び比較例１，２の
浴はＢｉの置換析出は起こらなかった・In addition, when the baths of Comparative Examples 3 and 4 immerse the object to be plated, Bi
However, in the baths of Examples and the baths of Comparative Examples 1 and 2, substitution precipitation of Bi did not occur.
Claims (1)
と、オキシカルボン酸とを含有し、かつビスマスと２価
の錫との含有割合が重量比として１：１〜１０：１であ
ることを特徴とするビスマス−錫合金電気めっき浴。 ２、請求項１記載のめっき浴を用いて被処理物に電気め
っきを施して、該被処理物にビスマス量が３０〜５５重
量％のビスマス−錫合金めっき皮膜を形成することを特
徴とするビスマス−錫合金電気めっき方法。[Claims] 1. Contains a bismuth salt, a divalent tin salt, an acid that dissolves the tin salt, and an oxycarboxylic acid, and the content ratio of bismuth and divalent tin is a weight ratio. A bismuth-tin alloy electroplating bath characterized in that the ratio is 1:1 to 10:1. 2. A workpiece is electroplated using the plating bath according to claim 1 to form a bismuth-tin alloy plating film containing 30 to 55% by weight of bismuth on the workpiece. Bismuth-tin alloy electroplating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238304A JPH0663110B2 (en) | 1988-09-22 | 1988-09-22 | Bismuth-tin alloy electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238304A JPH0663110B2 (en) | 1988-09-22 | 1988-09-22 | Bismuth-tin alloy electroplating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0288789A true JPH0288789A (en) | 1990-03-28 |
| JPH0663110B2 JPH0663110B2 (en) | 1994-08-17 |
Family
ID=17028216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63238304A Expired - Fee Related JPH0663110B2 (en) | 1988-09-22 | 1988-09-22 | Bismuth-tin alloy electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0663110B2 (en) |
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|---|---|---|---|---|
| US5674374A (en) * | 1993-06-01 | 1997-10-07 | Dipsol Chemicals Co., Ltd. | Sn-Bi alloy-plating bath and plating method using the same |
| US5759381A (en) * | 1995-09-07 | 1998-06-02 | Dipsol Chemicals Co., Ltd. | Sn-Bi alloy-plating bath and method for forming plated Sn-Bi alloy film |
| JP2006052421A (en) * | 2004-08-10 | 2006-02-23 | Ishihara Chem Co Ltd | Lead-free tin-bismuth based alloy electroplating bath |
| JP2006117980A (en) * | 2004-10-20 | 2006-05-11 | Ishihara Chem Co Ltd | Lead-free acidic tin-bismuth based alloy electroplating bath |
| JPWO2014188834A1 (en) * | 2013-05-20 | 2017-02-23 | ソニー株式会社 | Manufacturing method of plating film |
| JP2017212245A (en) * | 2016-05-23 | 2017-11-30 | 学校法人神奈川大学 | Method for manufacturing flexible thermoelectric conversion member |
| CN110777405A (en) * | 2018-07-25 | 2020-02-11 | 波音公司 | Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates |
| CN116845200A (en) * | 2023-07-10 | 2023-10-03 | 河南固锂电技术有限公司 | Magnesium ion battery negative electrode material and preparation method thereof |
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| JPS535034A (en) * | 1976-07-06 | 1978-01-18 | Dipsol Chem | Neutral electroplating bath for tin or tin alloy |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674374A (en) * | 1993-06-01 | 1997-10-07 | Dipsol Chemicals Co., Ltd. | Sn-Bi alloy-plating bath and plating method using the same |
| US5759381A (en) * | 1995-09-07 | 1998-06-02 | Dipsol Chemicals Co., Ltd. | Sn-Bi alloy-plating bath and method for forming plated Sn-Bi alloy film |
| JP2006052421A (en) * | 2004-08-10 | 2006-02-23 | Ishihara Chem Co Ltd | Lead-free tin-bismuth based alloy electroplating bath |
| JP2006117980A (en) * | 2004-10-20 | 2006-05-11 | Ishihara Chem Co Ltd | Lead-free acidic tin-bismuth based alloy electroplating bath |
| JPWO2014188834A1 (en) * | 2013-05-20 | 2017-02-23 | ソニー株式会社 | Manufacturing method of plating film |
| JP2017212245A (en) * | 2016-05-23 | 2017-11-30 | 学校法人神奈川大学 | Method for manufacturing flexible thermoelectric conversion member |
| CN110777405A (en) * | 2018-07-25 | 2020-02-11 | 波音公司 | Compositions and methods for electrodepositing tin-bismuth alloys on metal substrates |
| CN116845200A (en) * | 2023-07-10 | 2023-10-03 | 河南固锂电技术有限公司 | Magnesium ion battery negative electrode material and preparation method thereof |
| CN116845200B (en) * | 2023-07-10 | 2024-03-08 | 河南固锂电技术有限公司 | Magnesium ion battery negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0663110B2 (en) | 1994-08-17 |
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